Flame-retardant composition comprising a phosphonic acid derivative

ABSTRACT

The present invention relates to a flame-retardant composition that comprises a synergistic flame-retardant mixture, and a method for flame-retarding a polymer by adding the flame-retardant composition. The invention further relates to polymers that contain said flame-retardant composition.

This application is a division of Ser. No. 12/737,924, filed May 16,2011, which claims priority to PCT/EP2009/061489, filed Sep. 4, 2009,which claims priority to EP 08163790.2, filed Sep. 5, 2008.

The present invention relates to a flame-retardant composition thatcomprises a synergistic flame-retardant mixture, and a process forflame-retarding a polymer by adding this flame-retardant composition.The invention further relates to polymers that contain saidflame-retardant composition.

Today, polymers are frequently made flame-retardant by addingphosphorus- or halogen-containing compositions or mixtures to them.Mixtures of phosphorus- and nitrogen-containing compounds are now oftenused as flame-retardant agents. A problem usually accompanying this isthat the flame-retardant effect is too weak or the thermal stability ofthe resulting flame-retardant plastic is too low.

Furthermore, salts of phosphinic acids have been shown to be effectiveflame-retardant additives for polymers, and in such cases, both alkalimetal salts (DE-A 2 252 258) and salts of other metals (DE-A 2 447 727)are used. These flame-retardant additives produce minor changes in thethermal properties of the plastic, but they still show an insufficientflame-retardant effect.

The market for flame-retardant agents currently includes products thatact by interfering with all combustion processes through chemical orphysical processes. In this case, it has been shown that during thecombustion of an object, these agents act either in the gas phase, thecondensed phase, or in both phases. It is assumed that e.g. organichalogen forms (such as decabromodiphenyl oxide, hexabromocyclodecane(HBCD), and tetrabromobisphenol A) produce hydrogen halide (HX), whichinteracts with the free radical organic “fuel” from the polymersubstrate.

Synergists for reaction with HX have been suggested in order to formadditional chemical species which interfere with combustion in the gasphase, such as a reaction of antimony oxide with HX in order to generateantimony halide and hydrogen. Antimony compounds such as antimonytrioxide also act as radical scavengers in combination with halogencompounds. This can inhibit spreading of the fire. Although antimonycompounds and the typical halogen compounds are efficient with regard tothe cost-performance ratio, there have recently been numerous concernsabout toxicity of the byproducts that form during combustion in thepresence of a halogenated flame-retardant agent. Furthermore, antimonyoxides often contain trace amounts of arsenic compounds which aresuspected of being carcinogenic. Due to said disadvantages of thesecompounds, efforts are currently underway to replace antimony trioxideand bromine compounds in current commercial flame-retardantapplications. However, it is highly difficult to provide a substituteflame-retardant agent that is not only environmentally friendly but alsohighly efficient.

A further reason for adding flame-retardant compositions to polymers isto prevent dripping of parts of the polymer in the form of droplets asan effect of the fire. These droplets quite often catch fire themselvesand constitute a major hazard with respect to spreading of a fire.Therefore, a common measure is to add filling agents such as talcumpowder to the polymer in large amounts, which gives rise to certaindisadvantages concerning the mechanical properties of the polymer. Thefilling materials used in this case include calcium carbonate, magnesiumcarbonate, zinc borate, silicates, silicones, glass fibers, glass beads,asbestos, kaolin, barium sulfate, calcium sulfate, metal oxides,hydrides and hydroxides such as zinc oxide, magnesium hydroxide,aluminum oxide trihydrate, silicon dioxide, calcium silicate, andmagnesium silicates.

A publication that deals with the use of diphosphonates asflame-retardant compounds is U.S. Pat. No. 4,174,343. This documentdiscloses a large number of diphosphonates, which are said to haveflame-retardant properties in various polymers and copolymers.

Furthermore, hindered amines, which have long been used as light orthermal stabilizers for a large number of organic materials that aresusceptible to decomposition due to oxygen, heat, and actinic light haverecently been discussed as flame-retardant agents. Specifically, theseare various N-hydrocarbon oxy-substituted inhibited amines (so-called NRinhibited amines). For example, DE-T 69826477 discloses NR hinderedamines of this type that are said not only to have UV-stabilizing butalso flame-retardant properties.

With respect to prior art, the purpose of the invention is to provide anadditional highly-efficient and thermally stable flame-retardantcomposition. The components of the flame-retardant composition accordingto the invention must not adversely affect the thermal processability ofa plastic that has been made flame-retardant even at elevatedtemperatures in the range of approx. 250 to 300° C. Moreover, thecomponents of these flame-retardant compositions should interactsynergistically and therefore be suitable for concomitant use at lowerconcentrations compared to those required in the case of individualcomponents. The flame-retardant composition according to the inventionshould also be free of organic halogen compounds and heavy metals, thuspreventing exposure to toxic substances.

The invention achieves this purpose by comprising a blend or aflame-retardant composition containing a synergistic mixture of (A) and(B), which denote the following:

-   (A) is a compound or a mixture of 2 or more chemical compounds    selected from the group consisting of    -   a) one or more phosphonate compound(s) of the Formula

-   -   -   where A¹ and A² independently denote a substituted or            unsubstituted, straight or branched chain alkyl group having            1 to 4 carbon atoms, substituted or unsubstituted benzyl,            substituted or unsubstituted phenyl, or substituted or            unsubstituted naphthyl, and

    -   b) one or more phosphonate compound(s) of the following Formula

-   -   -   where A³ and A⁴ independently denote methyl or ethyl and A⁵            denotes a straight or branched chain alkyl group having 1 to            4 carbon atoms or a phenyl or benzyl group having up to 3            methyl groups respectively, and

    -   c) alkyl or arylphosphonic acids, where alkyl denotes a straight        or branched chain alkyl group having 1 to 4 carbon atoms, and        aryl denotes a substituted or unsubstituted benzyl, substituted        or unsubstituted phenyl, substituted or unsubstituted naphthyl,        or a salt or ester of the aforementioned phosphonic acid, and

-   (B) a 1,3,5-triazine compound or a mixture of two or more    1,3,5-triazine compound(s) selected from tris-2-hydroxyethyl    isocyanurate, melamine, melamine cyanurate, melamine phosphate,    poly-[2,4-(piperazin-1,4-yl)-6-(morpholin-4-yl)-1,3,5-triazine],    dimelamine phosphate, melamine pyrophosphate, and hindered amine    compounds of Formula I, II, IIA, and III:    R₁NH—CH₂CH₂CH₂NR₂CH₂CH₂NR₃CH₂CH₂CH₂NHR₄  (I)    T-E₁-T₁  (II)    T-E₁  (IIA)    G-E₁-G₁-E₁-G₂  (III),    -   where in the tetraamine of Formula I    -   R₁ and R₂ denote the s-triazine moiety E, and one of R₃ and R₄        denotes the s-triazine moiety E, with the other of R₃ or R₄        denoting a hydrogen,    -   E denotes

-   -   -   R denotes methyl, cyclohexyl or octyl,

    -   R₅ denotes an alkyl having 1 to 12 carbon atoms,

    -   where in the compound of Formula II or IIA, if R denotes        cyclohexyl or octyl,

    -   each of T and T₁ denotes a tetraamine substituted by R₁-R₄ as        defined in Formula I, where

    -   (1) one of the s-triazine moieties E in each tetraamine is        replaced by the group E₁, which forms a bridge between two        tetraamines T and T₁, or

    -   (2) the group E₁ can have both terminals in the same tetraamine        T as in Formula IIA, where two of the E moieties of the        tetraamine are replaced by one E₁ group, or

    -   (3) all three s-triazine substituents of tetraamine T can denote        E₁, such that one E₁ residue comprises the bond between T and T₁        and a second E₁ residue has both terminals in tetraamine T, and

    -   E₁ denotes

The blend itself may already be a flame-retardant composition, or incombination with other components to be specified below, constitute aflame-retardant composition.

According to a general embodiment of the invention, compound (B) may beone or more 1,3,5-triazine compound(s) selected from tris-2-hydroxyethylisocyanurate, melamine, melamine cyanurate, melamine phosphate,poly-[2,4-(piperazin-1,4-yl)-6-(morpholin-4-yl)-1,3,5-triazine],dimelamine phosphate, melamine pyrophosphate and hindered aminecompounds of the Formula I, II, III, IV, V, VI, VII, VIII, IX, X, or XI,

where in the case of a blend in (A), the components of the blend may beseveral, 2 or 3 compounds selected from the group (a), (b), and (c), andwhere the symbols have the following meaning:

E₁, E₂, E₃, and E₄ independently denote a linear or branched chain alkylhaving 1 to 4 carbon atoms, or E₁ and E₂ independently denote an alkylhaving 1 to 4 carbon atoms, and E₃ and E₄ taken together denotepentamethylene, or E₁ and E₂, and E₃ and E₄ each taken together denotepentamethylene,

R₁ denotes a linear or branched chain alkyl having 1 to 18 carbon atoms,a cycloalkyl having 5 to 12 carbon atoms, a bicyclic or tricyclichydrocarbon residue having 7 to 12 carbon atoms, a phenyl alkyl having 7to 15 carbon atoms, an aryl having 6 to 10 carbon atoms, or said arylsubstituted by 1 to 3 alkyls having 1 to 8 carbon atoms,

R₂ denotes hydrogen or a linear or branched chain alkyl having 1 to 12carbon atoms,

R₃ denotes an alkylene having 1 to 8 carbon atoms, or R₃ denotes —C(O)—,—C(O)—R₄—, —C(O)NR₂—, or —C(O)—NR₂—R₄—,

R₄ denotes an alkylene having 1 to 8 carbon atoms,

R₅ denotes hydrogen, a linear or branched chain alkyl having 1 to 12carbon atoms, or

or when R₄ denotes ethylene, two R₅ methyl substituents may be linked bya direct bond so that the triazine bridging group —N(R₅)—R₄—N(R₅)—denotes a piperazine-1,4-diyl moiety,

R₆ denotes alkylene having 2 to 8 carbon atoms, or R₆ denotes

with the proviso that Y is not —OH when R₆ has the structure depictedabove,

A denotes —O— or —NR₇—, where R₇ denotes hydrogen, a straight orbranched chain alkyl having 1 to 12 carbon atoms, or R₇ is

T denotes phenoxy, a phenoxy substituted by one or two alkyl groupshaving 1 to 4 carbon atoms, an alkoxy having 1 to 8 carbon atoms or—N(R₂)₂ with the stipulation that R₂ is not hydrogen, or T denotes

X denotes —NH₂, —NCO, —OH, —O-glycidyl, or —NHNH₂, and

Y denotes —OH, —NH₂, or —NHR₂ where R₂ is not hydrogen; or Y denotes—NCO, —COOH, oxiranyl, —O-glycidyl, or —Si(OR₂)₃; or the combinationR₃—Y— denotes CH₂CH(OH)R₂, where R₂ denotes an alkyl or said alkylinterrupted by one to four oxygen atoms, or R₃—Y— denotes CH₂OR₂; or

where the hindered amine compound denotes a mixture ofN,N′,N′″-tris{2,4-bis-[(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl)alkylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine;N,N′,N″-tris{2,4-bis[(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl)alkylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine, and bridged derivatives as described by FormulasI, II, IIA, and III,R₁NH—CH₂CH₂CH₂NR₂CH₂CH₂NR₃CH₂CH₂CH₂NHR₄  (I)T-E₁-T₁  (II)T-E₁  (IIA)G-E₁-G₁-E₁-G₂  (III),where in the tetraamine of Formula I,R₁ and R₂ are the s-triazine moiety E, and one of R₃ and R₄ denotes thes-triazine moiety E with the other of R₃ or R₄ being hydrogen,E denotes

R denotes methyl, propyl, cyclohexyl or octyl,R₅ denotes an alkyl having 1 to 12 carbon atoms,where in the compound of Formula II or IIA, when R denotes propyl,cyclohexyl or octyl,T and T₁ are each substituted by R₁-R₄ as defined for Formula I, where(1) one of the s-triazine moieties E in each tetraamine is replaced bythe group E₁, which forms a bridge between two tetraamines T and T₁,E₁ denotes

(2) the group E₁ can have both terminals in the same tetraamine T as inFormula IIA, where two of the E moieties of the tetraamine are replacedby one E₁ group, or(3) all three s-triazine substituents of tetraamine T can be E₁, suchthat one E₁ links T and T₁, and a second E₁ has both terminals intetraamine T;L denotes propanediyl, cyclohexanediyl or octanediyl;where in the compound of Formula III,

G, G₁, and G₂ are each tetraamines substituted by R₁-R₄ as defined forFormula I, except that G and G₂ each have one of the s-triazine moietiesE replaced by E₁, and G₁ has two of the triazine moieties E replaced byE₁, such that there is a bridge between G and G₁ and a second bridgebetween G₁ and G₂;

with said mixture being prepared by reacting two to four equivalents of2,4-bis[(1-hydrocarbyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-chloro-s-triazinewith one equivalent N,N′-bis(3-aminopropyl)ethylene diamine;

or the hindered amine denotes a compound of Formula IIIb

in which the index n ranges from 1 to 15;R₁₂ denotes C₂-C₁₂ alkylene, C₄-C₁₂ alkenylene, C₅-C₇ cycloalkylene,C₆-C₇ cycloalkylene-di(C₁-C₄ alkylene), C₁-C₄alkylenedi(C₅-C₇cycloalkylene), phenylenedi (C₁-C₄ alkylene) or C₄-C₁₂alkylene interrupted by 1,4-piperazinediyl, —O—, or >N—X₁, with X₁ beingC₁-C₁₂ acyl or (C₁-C₁₂ alkoxy) carbonyl or having one of the definitionsof R₁₄ given below except hydrogen; or R₁₂ denotes a group of theFormula (Ib′) or (Ic′);

and m being 2 or 3,with X₂ being C₁-C₁₈ alkyl, C₅-C₁₂ cycloalkyl that is unsubstituted orsubstituted by 1, 2 or 3 C₁-C₄ alkyls; phenyl that is unsubstituted orsubstituted by 1, 2 or 3 C₁-C₄ alkyls or C₁-C₄ alkoxys; C₇-C₉phenylalkyl that is unsubstituted or substituted on the phenyl by 1, 2or 3 C₁-C₄ alkyls; andthe X₃ residues independently denoting C₂-C₁₂ alkylene;R₁₃, R₁₄, and R₁₅, which are identical or different, are hydrogen,C₁-C₁₈ alkyl, C₅-C₁₂ cycloalkyl that is unsubstituted or substituted by1, 2, or 3 C₁-C₄ alkyl; C₃-C₁₈ alkenyl, phenyl that is unsubstituted orsubstituted by 1, 2 or 3 C₁-C₄ alkyls or C₁-C₄ alkoxys; C₇-C₉phenylalkyl that is unsubstituted or substituted on the phenyl by 1, 2,or 3 C₁-C₄ alkyls; tetrahydrofurfuryl or C₂-C₄ alkyl that is substitutedin the 2, 3, or 4 position by —OH, C₁-C₈ alkoxy, di(C₁-C₄alkyl)amino ora group of Formula (Ie′);

with Y being —O—, —CH₂—, —CH₂CH₂— or >N—CH₃,or —N(R₁₄)(R₁₅) additionally denotes a group of Formula (Ie′);the A residues independently denote —OR₁₃, —N(R₁₄)(R₁₅), or a group ofFormula (IIId)

X denotes —O— or >N—R₁₆;R₁₈ denotes hydrogen, C₁-C₁₈ alkyl, C₃-C₁₈ alkenyl, a C₅-C₁₂ cycloalkylthat is unsubstituted or substituted by 1, 2, or 3 C₁-C₄ alkyls; a C₇-C₉phenylalkyl that is unsubstituted or substituted on the phenyl by 1, 2,or 3 C₁-C₄ alkyls; tetrahydrofurfuryl, a group of the Formula (IIIf),

or C₂-C₄ alkyl that is substituted in the 2, 3, or 4 position by —OH,C₁-C₆ alkoxy, di(C₁-C₄ alkyl)amino, or a group of the Formula (Ie′);R₁₁ has one of the definitions given for R₁₆; andthe B residues independently have one of the definitions given for A.

In connection with the present invention, the substituents specified inthe following definitions have the following meaning:

the alkyl is straight or branched and denotes for example methyl, ethyl,n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl,2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl,n-tetradecyl, n-hexadecyl, or n-octadecyl.

Cycloalkyl groups include cyclopentyl and cyclohexyl; typicalcycloalkenyl groups include cyclohexyl.

According to a common embodiment of the invention, the one or morephosphonate compound(s) of component (A) are one or more phosphonatecompound(s) of the following Formula

where A¹ and A² independently denote a substituted or unsubstitutedstraight or branched chain alkyl group having 1 to 4 carbon atoms, asubstituted or unsubstituted benzyl, a substituted or unsubstitutedphenyl, or a substituted or unsubstituted naphthyl. According to anembodiment of the invention, the alkyl group may be a haloalkyl groupthat is substituted with one, two, or three halogen atoms selected fromchlorine and bromine. Furthermore, this may be a phenyl or ahalogen-substituted phenyl group such as 4-chlorophenyl,2,4-dichlorophenyl, 2,4,6-trichlorophenyl, 4-bromophenyl,2,4-dibromophenyl, or 2,4,6-tribromophenyl. Moreover, A¹ and A² mayindependently denote phenylalkyl having 7 to 9 carbon atoms orphenylalkenyl having 8 to 10 carbon atoms, which may be substituted inthe alkyl residue. Further phosphonate compounds of the above formulasare disclosed in U.S. Pat. No. 4,174,343 and DE 26 30 693, thedisclosures of which are incorporated herein by reference.

According to a further preferred embodiment of the invention, thephosphonate compound (A) contained in the flame-retardant composition isa composition of the following structural Formula

wherein A¹ and A² independently denote an alkyl having 1 to 4 carbonatoms, preferably a methyl group, an ethyl group or a propyl group, withan alkyl having 1 to 2 carbon atoms being particularly preferable and amethyl group being most preferable. In a particularly preferredembodiment, the phosphonate is dimethylspirophosphonate, in which thesubstituents A¹ and A² of the aforementioned Formula are methyl groups.

According to a common embodiment of the invention, the one or morephosphonate compound(s) of component (A) are one or more phosphonatecompound(s) of Formula

wherein A³ and A⁴ independently denote methyl or ethyl and A₅ denotes astraight or branched chain alkyl group having 1 to 4 carbon atoms or aphenyl or benzyl group, each of which may have up to 3 methyl groups.According to a preferred embodiment of the invention, the compound orcompound(s) of the above formula is/are a compound that is disclosed inU.S. Pat. No. 4,228,063, U.S. Pat. No. 3,966,894, and U.S. Pat. No.512,373. The compounds disclosed in these documents are included byreference in the disclosure of the present invention.

According to a more preferred embodiment of the invention, the one ormore phosphonate compound(s) are compounds of the following Formula

wherein A³ and A⁴ independently denote methyl or ethyl and A⁵ denotes astraight or branched chain alkyl group having 1 to 4 carbon atoms or aphenyl or benzyl group that may have up to 3 methyl groups each.According to a preferred embodiment of the invention, A³ and A⁴ aremethyl groups and A⁵ denotes an alkyl group having 1 to 3 carbon atoms.According to a particularly preferred embodiment of the invention, allthree substituents A³, A⁴, and A⁵ are methyl groups.

According to another preferred embodiment of the invention, thephosphonate compound contained in the mixture or in the flame-retardantcomposition is an alkylphosphonic acid, and particularly preferably amethane phosphonic acid, ethane phosphonic acid, propane phosphonicacid, or a derivative thereof such as a salt or ester thereof. In thiscase, the salt may be an ammonium salt, guanidinium salt, DCDA,guanylurea, melamine, ethylene diamine or a piperazine salt. If themethane phosphonic acid is in the form of an ester, this may be analkylester having 1 to 3 carbon atoms. It should preferably be amethyl-, ethyl-, propyl- or trimethylol propane, substituted orunsubstituted aryl, substituted or unsubstituted benzyl, or substitutedor unsubstituted phenyl ester of the alkyl phosphonic acid. Preferredexamples include the following commercially available esters, such as3-(dimethylphosphono)-propionic acid-methylolamide, available under thetrade name Amgard CU from Rhodia Inc. AFLAMMIT KWB from THOR GmbH,Speyer, Amgard CT from Rhodia Inc., AFLAMMIT PE conc. from THOR GmbH,Speyer, Amgard V 490 from Rhodia Inc., AFLAMMIT TL 1002 from THOR GmbH,Speyer, Fyrol PMP from Akzo, FRX 100 from FRX Polymers, Levagard DMPPfrom Clariant, and Exolit OP 560 from Clariant. According to anothercommon embodiment of the invention, the phosphonate compound contains aphenylphosphonic acid, e.g. Fyrol PMP, available from Akzo Nobel, or FRX100, available from FRX Polymers.

According to an embodiment of the invention, the mixture or theflame-retardant composition of the invention also includes one or moreradical formers.

In the framework of the present invention, the term radical former isunderstood to denote a compound capable of releasing a radical compoundby chemical or physical means. It is preferable that the radicalcompound here involves a Br radical, Cl radical, or H radical. Anexample of this type of radical compound is a compound that can releasebromine and/or chlorine and/or hydrogen in the form of the respectivefree radical. According to a preferred embodiment of the invention, theradical former is NH₄Br or NH₄Cl. The radical former may be either aninorganic or an organic compound. According to another embodiment of theinvention, the radical former can involve a halogenated flame retardant.According to another embodiment of the invention, the 1,3,5-triazinecompounds (B) are used in the form of their hydrobromines orhydrochlorides.

The amount of the radical former with respect to the 1,3,5-triazinecompound(s) B can vary over a wide range. The amount is generallyselected in such a manner that 0.001 to 1,000 mol of the radicals, andpreferably 0.01 to 100 mol, are formed per mole of the 1,3,5-triazinecompound, with an amount of 0.1 to 10 mol of radicals being particularlypreferred.

According to an embodiment of the invention, the 1,3,5-triazine compound(B) contained in the flame-retardant composition is melamine, accordingto a preferred embodiment of the invention in combination with a radicalformer. According to a particularly preferred embodiment of theinvention, the 1,3,5-triazine compound, i.e. the melamine, is in theform of the hydrobromide or hydrochloride.

According to another embodiment of the invention, the 1,3,5-triazinecompound (B) contained in the flame-retardant composition is melaminecyanurate, according to a preferred embodiment of the invention incombination with a radical former.

According to another embodiment of the invention, the 1,3,5-triazinecompound (B) contained in the flame-retardant composition is melaminephosphate, according to a preferred embodiment of the invention incombination with a radical former.

According to another embodiment of the invention, the 1,3,5-triazinecompound (B) contained in the flame-retardant composition is dimelaminephosphate, according to a preferred embodiment of the invention incombination with a radical former.

According to another embodiment of the invention, the 1,3,5-triazinecompound (B) contained in the flame-retardant composition is melaminepyrophosphate and/or melamine polyphosphate, according to a preferredembodiment of the invention in combination with a radical former.

According to another embodiment of the invention, the 1,3,5-triazinecompound (B) contained in the flame-retardant composition ispoly-[2,4-(piperazin-1,4-yl)-6-morpholin-4-yl]-1,3,5-triazine], knownunder the trade name ppm-Triazine™, available from Evonik Industries.According to a preferred embodiment of the invention, thepoly-[2,4-(piperazin-1,4-yl)-6-morpholin-4-yl]-1,3,5-triazine] is usedin combination with a radical former.

According to another embodiment of the invention, the 1,3,5-triazinecompound (B) contained in the flame-retardant composition istris-2-hydroxyethyl isocyanurate, known under the trade name THEIC™,available from BASF SE. Compositions containing tris-2-hydroxyethylisocyanurate and one or more compounds of Group Aa) and/or Ab) alsostand out for their usefulness as hot-melt adhesives.

According to another embodiment of the invention, the 1,3,5-triazinecompound (B) contained in the flame-retardant composition is a hinderedamine compound having above Formula I, II, III, IV, V, VI, VII, VIII,IX, X, or XI.

According to another embodiment of the invention, the 1,3,5-triazinecompound (B) contained in the flame-retardant composition is a compoundavailable under the trade names Budit 310, Budit 311, Budit 312, Budit314, and Budit 3141 from Budenheim KG, Germany, or PPM Triazine™ fromEvonik Industries, Germany. According to a preferred embodiment of theinvention, the aforementioned compounds may be used in combination witha radical former.

According to another embodiment of the invention, the 1,3,5-triazinecompound (B) contained in the flame-retardant composition is a hinderedamine compound marketed under the trade name FLAMESTAB NOR 116 by Ciba.This flame-retardant agent is disclosed in EP 0 889 085, the disclosuresof which are incorporated herein by reference. Flamestab NOR comprisesone or more compound(s) selected from the groupR₁NH—CH₂CH₂CH₂NR₂CH₂CH₂NR₃CH₂CH₂CH₂NHR₄  (I)T-E₁-T₁  (II)T-E₁  (IIA)G-E₁-G₁-E₁-G₂  (III),where in the tetraamine of Formula IR₁ and R₂ denote the s-triazine moiety E; and one of R₃ and R₄ denotesthe s-triazine moiety E, with the other of R₃ and R₄ denoting hydrogen,where E denotes

R denotes cyclohexyl,R₅ denotes an alkyl having 1 to 12 carbon atoms,where in the compound of Formula II or IIA, when R denotes cyclohexyl, Tand T₁ are each a tetraamine substituted by R₁-R₄ as defined for FormulaI, where(1) one of the s-triazine moieties E in each tetraamine is replaced bythe group E₁ which forms a bridge between two tetraamines T and T₁,E₁ is

The hindered amine compounds shown above according to Formulas I, II,IIA, and III can also contain a mixture ofN,N′,N′″-tris{2,4-bis[(1-hydrocarbonoxy-2,2,6,6-tetramethylpiperidin-4-yl)alkylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine; andN,N′,N″-tris{2,4-bis[(1-hydrocarbonoxy-2,2,6,6-tetramethylpiperidin-4-yl)alkylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine.

The combination of the above-defined 1,3,5-triazine compound(s)(Flamestab NOR™) with the dimethylspirophosphonate (A) provides asynergistic flame-resistant compound that shows high efficacy even whenused in small amounts.

The synergistic effect of the flame-resistant composition of theinvention is clearly greater than the commonly observed additive effectof the individual Components (A) and (B). For example, it wassurprisingly found that by concomitantly using Components (A) and (B) asflame-resistant components, it becomes possible to use these componentsto impart flame resistance to plastics in substantially lower amountsthan in the case of an additive effect.

A flame-retardant composition comprising Components (A) and (B) in theweight ratios given below is referred to in the following as a“flame-retardant composition according to the invention.” A“flame-retardant composition according to the invention” may contain oneor more additional components other than Components (A) and (B) asflame-retardant components in the weight ratios specified below. Theadditional component or components may have a flame-retardant action, orthey may have no flame-retardant action, e.g., they could be an additivefor example.

In another embodiment of the invention, the flame-retardant compositionaccording to the invention essentially comprises Components (A) and (B)as flame-retardant active components, i.e., in addition to Components(A) and (B), the composition may contain one or more otherflame-retardant components, but these must be present in amounts suchthat they do not make any contribution to the overall effect of theresulting mixture. This means that if the flame-retardant effect of aflame-retardant composition according to the invention that—in additionto Components (A) and (B) as essential constituents—also contains onemore additional flame-retardant components in subordinate or minorconcentrations is not modified with respect to use of theflame-retardant composition of the invention, this will be described inconnection with the present invention with the wording “essentiallycomprising.”

In another embodiment, the flame-retardant composition may compriseComponents (A) and (B) as its only flame-retardant components. In such acase, it is only possible for one or more additional components nothaving a flame-retardant effect to be present, for example, commonadditives that are described in greater detail below.

The ratio (in parts by weight) of Compound(s) (A) to Compound orCompounds (B) is selected in such a manner that the flame-retardanteffect of the two components is synergistic. In this case, for example,the ratio in the composition is between 1:100 and 100:1, and preferablyin the range of 1:10 to 10:1, with a range of 3:7 to 7:1 beingparticularly preferred. In this case, the amount of Component (A) andComponent (B) used also depends on the efficacy of the particularcompound(s) and the particular area of application.

The composition according to the invention may also include acidscavengers. Examples of acid scavengers include hydrotalcite andamorphous basic aluminum magnesium carbonates such as those described inU.S. Pat. No. 4,427,816 and U.S. Pat. No. 5,234,981. Hydrotalcite isalso known as Hycite or DHT4A. The hydrotalcites can be natural orsynthetic. It is assumed that natural hydrotalcite will have thestructure Mg₆Al₂(OH)₁₈CO₃×4H₂O.

The flame-retardant composition according to the invention or thepolymer containing this flame-retardant composition according to theinvention may also contain additives. One example of such additives areacid scavengers, which may be present in the polymer composition forexample in an amount of 0.1 to 1.0% by weight with respect to the weightof the polymer composition. For example, these acid scavengers may bepresent in the amount of 0.2 to 0.8 or 0.4 to 0.6% by weight withrespect to the weight of the polymer composition.

In this case, the acid scavengers support the present composition incolor, odor, and stability.

The polymers or polymer compositions or the flame-retardant compositionaccording to the present invention may also contain additionaladditives. These additional additives are chiefly obtained from thegroup of the heat stabilizers and/or light stabilizers. In this case,thermal stabilization includes both processing and use (long-termstability). Such additives are known to a person skilled in the art, andmost of them are commercially available. Examples of suitable additivesinclude the following:

Antioxidants such as

alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol,2-tert-butyl-4,6-di-methylphenol, 2,6-di-tert-butyl-4-ethylphenol,2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol,2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonyl phenols that are linearor branched in the side chains, for example 2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-di-methyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol, and mixtures thereof.

Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol, and2,6-didodecyl-thiomethyl-4-nonylphenol.

Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, and bis-(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.

Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol, and mixtures thereof (vitamin E).

Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol).4,4′-thiobis-(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.

Alkylidene bisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butyl-phenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,and 1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, andisooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,andbis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

Aromatic hydroxybenzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,and 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

Triazine compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,and 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, and thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, and octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexane diol, 1,9-nonane diol, ethyleneglycol, 1,2-propane diol, neopentyl glycol, thiodiethylene glycol,diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyl-ethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexane diol, trimethylolpropane, and 4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane.

Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexane diol, 1,9-nonane diol, ethyleneglycol, 1,2-propane diol, neopentyl glycol, thiodiethylene glycol,diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexane diol, trimethylolpropane, and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexane diol, 1,9-nonane diol, ethylene glycol,1,2-propane diol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexane diol,trimethylolpropane, and4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- orpolyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol,1,6-hexane diol, 1,9-nonane diol, ethylene glycol, 1,2-propane diol,neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethyleneglycol, pentaerythritol, tris(hydroxyethyl)isocyanurate,N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,trimethylhexane diol, trimethylolpropane, and4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)trimethylenediamide, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazide,andN,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard® XL-1 supplied by Uniroyal).

Ascorbic acid (vitamin C).

Aminic antioxidants, for example N,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyidiphenylamine, 4-isopropoxy-diphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for example,p,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono-und dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono-und dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono-und dialkylatedtert-octyl-phenothiazines, N-allylphenothiazine,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis-(2,2,6,6-tetramethyl-piperid-4-yl)-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)-sebacate,2,2,6,6-tetramethylpiperidin-4-one, and2,2,6,6-tetramethylpiperidin-4-ol.

UV absorbers and light stabilizers, such as2-(2-hydroxyphenyl)-2H-benzotriazoles, for example known commercialhydroxyphenyl-2H-benzotriazoles and benzotriazoles as disclosed in U.S.Pat. Nos. 3,004,896; 3,055,896; 3,072,585; 3,074,910; 3,189,615;3,218,332; 3,230,194; 4,127,586; 4,226,763; 4,275,004; 4,278,589;4,315,848; 4,347,180; 4,383,863; 4,675,352; 4,681,905, 4,853,471;5,268,450; 5,278,314; 5,280,124; 5,319,091; 5,410,071; 5,436,349;5,516,914; 5,554,760; 5,553,242; 5,574,166; 5,607,987, 5,977,219 and6,166,218 such as 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3,5-di-t-butyl-2-hydroxyphenyl)-2H-benzotriazole,2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole,2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole,5-chloro-2-(3,5-di-t-butyl-2-hydroxyphenyl)-2H-benzotriazole,5-chloro-2-(3-t-butyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3-sec-butyl-5-t-butyl-2-hydroxyphenyl)-2H-benzotriazole,2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole,2-(3,5-di-t-amyl-2-hydroxyphenyl)-2H-benzotriazole,2-(3,5-bis-α-cumyl-2-hydroxyphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-(ω-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)phenyl)-2H-benzotriazole,2-(3-dodecyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-octyloxycarbonyl)ethylphenyl)-2H-benzotriazole,dodecylated 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-octyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,2-(3-tert-butyl-5-(2-(2-ethylhexyloxy)-carbonylethyl)-2-hydroxyphenyl)-5-chloro-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-2H-benzotriazole,2-(3-t-butyl-5-(2-(2-ethylhexyloxy)carbonylethyl)-2-hydroxyphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl-2H-benzotriazole,2,2′-methylene-bis(4-t-octyl-(6-2H-benzotriazol-2-yl)phenol),2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,2-(2-hydroxy-3-t-octyl-5-α-cumylphenyl)-2H-benzotriazole,5-fluoro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3,5-di-t-octylphenyl)-2H-benzotriazole,methyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyhydrocinnamate,5-butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-t-butylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,5-butylsulfonyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole, and5-phenylsulfonyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole.

2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy,and 2′-hydroxy-4,4′-dimethoxy derivatives.

Esters of substituted and unsubstituted benzoic acids, such as4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, and2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

Acrylates, for example ethyl-α-cyano-β,β-diphenylacrylate,isooctyl-α-cyano-β,β-diphenylacrylate, methyl-α-carbomethoxycinnamate,methyl-α-cyano-β-methyl-p-methoxy-cinnamate,butyl-α-cyano-β-methyl-p-methoxy-cinnamate,methyl-α-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

Nickel compounds, for example nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine, or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, and nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate,the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cycliccondensates ofN,N′-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensates of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]);N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decaneand epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,diester of 4-methoxymethylene-malonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,reaction product of maleic acid anhydride-α-olefin-copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine.

Oxamides, for example 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide,2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2-(2-Hydroxyphenyl)-1,3,5-triazines, for example known commercialtris-aryl-o-hydroxyphenyl-s-triazines and triazines as disclosed in WO96/28431 and U.S. Pat. Nos. 3,843,371; 4,619,956; 4,740,542; 5,096,489;5,106,891; 5,298,067; 5,300,414; 5,354,794; 5,461,151; 5,476,937;5,489,503; 5,543,518; 5,556,973; 5,597,854; 5,681,955; 5,726,309;5,736,597; 5,942,626; 5,959,008; 5,998,116; 6,013,704; 6,060,543;6,187,919; 6,242,598 and 6,255,483, for example4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-octyloxyphenyl)-s-triazine,Cyasorb® 1164, Cytec Corp,4,6-bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)-phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine,2,4-bis(4-biphenylyl)-6-(2-hydroxy-4-octyloxycarbonylethylideneoxyphenyl)-s-triazine,2-phenyl-4-[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-6-[2-hydroxy-4-(3-sec-amyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-benzyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,2,4-bis(2-hydroxy-4-n-butyloxyphenyl)-6-(2,4-di-n-butyloxyphenyl)-s-triazine,2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy*-2-hydroxypropyloxy)-5-α-cumylphenyl]-s-triazine(* denotes a mixture of octyloxy, nonyloxy and decyloxy groups),methylenebis-{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butyloxy-2-hydroxypropoxy)phenyl]-s-triazine},methylene bridged dimer mixture bridged in the 3:5′, 5:5′ and 3:3′positions in a 5:4:1 ratio,2,4,6-tris(2-hydroxy-4-isooctyloxycarbonylisopropylideneoxy-phenyl)-s-triazine,2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-hexyloxy-5-α-cumylphenyl)-s-triazine,2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,2,4,6-tris[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,a mixture of4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-dodecyloxy-2-hydroxypropoxy)-phenyl)-s-triazineand4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-tridecyloxy-2-hydroxypropoxy)-phenyl)-s-triazine,Tinuvin® 400, Ciba Specialty Chemicals Corp.,4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-(2-ethylhexyloxy)-2-hydroxypropoxy)-phenyl)-s-triazine,and 4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine.

Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

Phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite,trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritoldiphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritoldiphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritoldiphosphite, diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylenediphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,2,2′,2″-nitrilo[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′,diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite.

Especially preferred are the following phosphites:Tris(2,4-di-tert-butylphenyl)phosphite (Irgafos® 168, Ciba-Geigy) andtris(nonylphenyl)phosphite.

Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, and N,N-dialkylhydroxylaminederived from hydrogenated tallow amine.

Nitrones, for example, N-benzyl-α-phenyl-nitrone,N-ethyl-α-methyl-nitrone, N-octyl-α-heptyl-nitrone,N-lauryl-α-undecyl-nitrone, N-tetradecyl-α-tridcyl-nitrone,N-hexadecyl-α-pentadecyl-nitrone, N-octadecyl-α-heptadecyl-nitrone,N-hexadecyl-α-heptadecyl-nitrone, N-octadecyl-α-pentadecyl-nitrone,N-heptadecyl-α-heptadecyl-nitrone, N-octadecyl-α-hexadecyl-nitrone, andnitrone derived from N,N-dialkylhydroxylamine derived from hydrogenatedtallow amine.

Thiosynergists, for example, dilauryl thiodipropionate or distearylthiodipropionate.

Peroxide scavengers, for example esters of β-thiodipropionic acid, forexample the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, and pentaerythritoltetrakis(β-dodecylmercapto)propionate.

Polyamide stabilizers, for example, copper salts in combination withiodides or phosphorus compounds and salts of divalent manganese.

Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallylcyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids, for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate, or zincpyrocatecholate.

Nucleating agents, for example, inorganic substances such as talcum,metal oxides such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; and polymeric compounds such as ioniccopolymers (ionomers).

Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibers, glass bulbs, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, and syntheticfibers.

Other additives, for example, plasticizers, lubricants, emulsifiers,pigments, rheology additives, catalysts, flow-control agents, opticalbrighteners, flameproofing agents, antistatic agents, and blowingagents.

Benzofuranones and indolinones, for example those disclosed in U.S. Pat.No. 4,325,863; U.S. Pat. No. 4,338,244, U.S. Pat. No. 5,175,312; U.S.Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4316611; DE-A-4316622;DE-A-4316876; EP-A-0589839 or EP-A-0591102 or3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, and3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

Examples of suitable lubricants include montan wax, fatty acid esters,PE waxes, amide waxes, polyol partial esters, partially saponified PEwaxes, so-called complex ester chloroparaffins, glycerol esters, andalkaline earth metal soaps or fatty ketones, such as described inDE4204887. Suitable lubricants are also described in “Taschenbuch derKunststoffadditive”, editors R. Gächter and H. Muller, Hanser Verlag,3^(rd) edition, 1990, pages 443-503. Other lubricant embodiments, inparticular combinations of lubricants, are to be found in EP 0 062 813and EP 0 336 289.

The present composition can additionally contain another UV absorberselected from the group consisting of the s-triazines, the oxanilides,the hydroxybenzophenones, benzoates and the α-cyanoacrylates.Specifically, the present composition may additionally contain aneffective stabilizing amount of at least one other2-hydroxyphenyl-2H-benzotriazole, another tris-aryl-s-triazine, or ahindered amine or mixtures thereof. For example, additional componentsare selected from pigments, dyes, plasticizers, antioxidants,thixotropic agents, leveling auxiliaries, basic costabilizers,additional light stabilizers such as UV absorbers or sterically hinderedamines, metal passivators, metal oxides, organophosphorus compounds,hydroxylamines, and mixtures thereof, particularly pigments, phenolicantioxidants, calcium stearate, zinc stearate, phosphite and phosphonitestabilizers, UV absorbers of the 2-(2′-hydroxyphenyl)benzotriazole and2-(2-hydroxyphenyl)-1,3,5-triazine classes, and sterically hinderedamines.

The present invention also concerns the use of the flame-retardantcomposition of the invention for flame-retardant finishing of polymersor polymer blends. In this case, the polymer or polymer substrate can beany of a wide variety of polymer types, including polyolefins,polyesters, polyamides, or ABS polymers. Highly preferred polymers arepolypropylene, polyethylene, thermoplastic olefin (TPO), ABS, andhigh-impact polystyrene; particularly preferred polymers arepolypropylene, polyethylene, and thermoplastic olefin (TPO),thermoplastic polyurethane elastomers (TPU), polyvinylchloride (PVC),polyvinyl acetate (PVA), ethyl vinyl acetate (EVA), polyester resins(UP-Resins), polyureas, and polyurethanes.

The effective flame-retardant amount of the flame-retardant compositionaccording to the invention is the amount required to show aflame-retardant effect, and this amount is measured by means of one ofthe standard procedures used for evaluation of flame-retardingproperties. These include the NFPA 701 Standard Procedure for FlameTesting of Flame-Resistant Textiles and Films, 1989 and 1996 Editions;the Electro-UL 94-Test for Flammability of Plastic Materials forComponents in Equipment and Devices, 5th Edition, 29 Oct. 1996, LimitingOxygen Index (LOI), ASTM-D2863, and Cohen calorimetry ASTM E-1354.Moreover, the standards for buildings (DIN4102B1) and motor vehicles(MVSS 302) may be used to investigate the flame-retardant properties ofthe flame-retardant composition according to the invention.

The present invention thus also concerns a flame-retardant compositioncomprising:

(a) a polymer and

(b) an effective flame-retardant amount of the synergisticflame-retardant composition according to the invention.

The effective flame-retardant amount of the flame-retardant compositionshould appropriately be 0.1 to 60% by weight with respect to thepolymer, and preferably 0.5 to 30% by weight, with an amount of 1 to 10%by weight being particularly preferred.

The flame-retardant polymers containing the flame-retardant compositionsaccording to the invention may be manufactured by means of knownmethods, for example by mixing the aforementioned additives andoptionally additional additives with the polymer using equipment such ascalenders, mixers, kneaders, extruders and the like. The additives maybe added individually or mixed with one another. It is also possible touse so-called masterbatches. In such processes, for example, the polymermay be used in the form of powders, granulates, solutions, suspensions,or in the form of lattices. The finished polymer compositions obtainedin this manner, which have been made flame-retardant, can be made intothe desired form by means of known methods. Such methods includecalendering, extruding, injection molding, spray coating, flexibladecoating, spinning, compression melting, rotary molding, thermoforming,or extrusion blowing. The finished flame-retardant polymer can also beprocessed into foamed objects.

Examples of polymer objects manufactured in this manner include fibers,films and foils, molded objects, and foamed molding products.

The additives according to the invention and optionally other componentsmay be added to the polymer material individually or mixed with oneanother. If desired, the individual components may be mixed with oneanother before being added to the polymer, for example by dry mixing,compacting, or in a smelter.

According to another embodiment, the invention concerns a process forimparting flame-retardant properties to a polymer, in which the processcomprises the addition of Components (A) (one or more diphosphonatecompound(s)) and (B) (one or more 1,3,5-triazine compound(s)) to thepolymer. In this case, the effective flame-retardant amount ofComponents (A) and (B) is the amount required to demonstrateflame-retardant efficacy, and this amount can be measured by means ofone of the aforementioned standard procedures. The following examplesare only given for explanatory purposes and not in any way to limit thescope of the invention. Unless otherwise specified, room temperaturerefers to a range of 20 to 25° C. Percentages refer to the weight of thepolymer substrate, unless otherwise specified.

The following examples explain the invention in further detail.

In order to demonstrate the invention, polyethylene films mixed withvarious flame-retardant compositions were manufactured.

1. Manufacture of Powder Mixtures:

A precise amount of polyethylene powder, Pallman 500/1 Extruder, andpowder mixtures of the flame-retardant agents according to Examples 1through 23 (for example, 98 g of polymer and 2 g of flame-retardantagent) were mixed and homogenized using a laboratory mixer. The powdermixtures were dried for 2 hours at 80° C.

2. Manufacture of Films:

The films were manufactured on a single-screw extruder 19/25Dmanufactured by Brabender Corp. at a melt temperature of 210° C. and arotation speed at which a maximum of 50% of the torque was reached.

In this case, the powder mixtures according to Examples 1 through 23were manually added using a funnel. The tool used was a broad-bandnozzle head 100×0.5 mm, and the discharge belt was adjusted so as toachieve a film width of 90 mm and a thickness of 0.20 mm. Air coolingwas then carried out.

3. Assessment of Efficacy

In order to test the flame-retardant agent, the following tests wereconducted on the films manufactured according to 2. above:

Determination of the LOI value according to DIN ISO 4589 on an LOI testunit manufactured by Raczek Corp.

Combustion test according to DIN 53438 Part 3.

For these purposes, test pieces measuring 230 mm×90 mm weremanufactured. These were then placed vertically in a combustion chamber.Combustion took place on a flat surface with a flame height of 20 mm anda flame angle of 45°.

Note: this DIN corresponds to DIN 4102-B2, provided that the uppermeasurement mark of the combustion test piece is not reached by the tipof the flame or it goes out on its own.

COMPARISON EXAMPLES 0 AND 1

98 g of polyethylene powder and 0 or 2 g of dimethylspirophosphonaterespectively were homogenously mixed according to the above process. Asufficient amount of film to carry out the flame-retardant propertiestests was manufactured from this mixture.

EXAMPLES 3 THROUGH 10, 12 AND 13, 15 THROUGH 17, 19, AND 21 THROUGH 23,25 AND 26 AND COMPARISON EXAMPLES 2, 11, 14, 18, 20, 24, AND 27

Examples and Comparison Examples 2 through 25 were carried out in thesame manner, and the results of Examples and Comparison Examples 0through 25 are summarized in the following Table.

Pallmann NOR Domus Melamine PPM, LOI Burn-in depth Expl 500-1 DMSP*EAP** MP*** 116 Melamine BM 41 cyanurate Triazine THEIC (%) (mm) 0 100 —— — — — — — — — 22.0 Burns off 1 98 g 2 g — — — — — — — — 25 Burns off 298 g — — —  2 g — — — — — 25 Burns off 3 98 g 1 g — —  1 g — — — — —28.5 100 4 98 g 0.5 g  — — 1.5 g — — — — — 29.2  80 5 98 g 1.5 g  — —0.5 g — — — — — 29.9  70 6 98.5 g 1 g — — 0.5 g — — — — — 28.0  80 798.7 g 1 g — — 0.3 g — — — — — 27.5 100 8 98 g —  2 g — — — — — — — 29 70 9 98 g 1.5 g — 0.5 g — — — — — 33  55 10 98.7 g — 1 — 0.3 — — — — —30.5  60 11 98 g — — 2 — — — — — — 26.5 Burns off 12 98 g — — 1.5 0.5 —— — — — 30.5  90 13 98.7 g — — 1 0.3 — — — — — 29.0  95 14 98 g — — — — 2 g — — — — 23.7 Burns off 15 98 g 1 g — — —  1 g — — — — 28.0 100 1698 g 1.5 g  — — — 0.5 g — — — — 29.3  90 17 98.7 g 1 g — — — 0.3 g — — —— 26.9 110 18 98 g — — — — — 2 g — — — 23.5 Burns off 19 98 g 1 g — — —— 1 g — — — 28.7 100 20 98.7 g 1 g — — — — 0.3 g  — — — 27.0 110 21 98 g— — — — — — 2 g — — 23.4 Burns off 22 98 g 1 g — — — — — 1 g — — 25.9120 23 98.7 1 g — — — — — 0.3 g  — — 25.1 125 24 98 — — — — — — —  2 g —23.2 Burns off 25 98.5 1 g — — — — — — 0.5 g — 26.8 110 26 98.5 g 1 g —— — — — — — 0.5 27.5 130 27 98.0 g — — — — — — — — 2.0 25 Burns offDMSP*: dimethylspirophosphonate EAP**: Ethylene diamine methanephosphonate MP***: Melamine methane phosphonate: Domus HM 41 ™: Melaminehydrobromide ppm-Triazine ™:Poly-[2,4-(piperazin-1,4-yl)-6-(morpholin-4-yl)-1,3,5-triazine THEIC:Tris-2-hydroxyethylisocyanurate NOR 116: FLAMESTAB NOR 116 from Ciba

As can be seen from the results shown in Table 1, the foils manufacturedaccording to Comparison Examples 1, 2, 11, 14, 18, 21, 24, and 27 didnot show satisfactory results in the combustion tests. One can clearlysee from the results of Examples 3 through 10, 12 and 13, 15 through 17,19, and 21 through 26 that the present invention provides synergisticflame-retardant agents that show a flame-retardant effect compared touse of the individual components, even when used in a low concentration.

For example, this can be clearly shown with reference to ComparisonExamples 1 and 2 and Examples 3 through 7. While the use of DMSP(Comparison Example 1) or NOR 116 (Comparison Example 3) in amounts of2% by weight each yielded an LOI value of 25, the use of 1% by weighteach caused the LOI value to increase to a value of 28.5 (Example 3).Even the reduction of a single component, the NOR 116 in Example 7,still led to an LOI value of 27.5, which is distinctly higher than thevalues of Comparison Examples 1 and 2 (LOI=25 in both cases). Thisclearly shows that this is a synergistic flame-retardant composition.

The amount of flame-retardant agent with respect to the finished polymercompound that is necessary in order to reach the LOI of the respectiveindividual substance can be sharply reduced by using the synergisticflame-retardant composition. By using this synergistic composition, itis thus possible, based on the low percentage of the flame-retardantcomposition required, to manufacture thin-walled molding compounds ornonwoven materials that meet the requirements of the necessary fireprotection class.

The invention claimed is:
 1. A blend comprising a synergistic mixture of(A) and (B), wherein: (A) is a chemical compound or a mixture of two ormore chemical compounds of one or more phosphonate compound(s) accordingto the following formula

wherein A¹ and A² are each independently of the other a substituted orunsubstituted straight chain or branched chain alkyl group having 1 to 4carbon atoms, a substituted or unsubstituted benzyl, a substituted orunsubstituted phenyl, or a substituted or unsubstituted naphthyl, and(B) a 1,3,5-triazine compound beingpoly-[2,4-(piperazine-1,4-yl)-6-(morpholine-4-yl)-1,3,5-triazine]. 2.The blend according to claim 1, wherein the phosphonate compound being acompound of the following formula


3. The blend according to claim 1, further comprisingN,N′,N′″-tris{2,4-bis[(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl)alkylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamineandN,N′,N″-tris-{2,4-bis[(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl)alkylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine.4. The blend according to claim 1, wherein the phosphonate compound(s)(A) and the 1,3,5-triazine compound(s) (B) are in a ratio of 1:100 up to100:1.
 5. A flame-retardant composition comprising a mixture accordingto claim 1 as well as possibly one or more further component(s),selected from the group consisting of pigments, colorants, softeners,antioxidants, phenolic antioxidants, thixotropic agents, levellingagents, basic co-stabilizers, nitrone stabilizers, amine oxidestabilizers, benzofurane stabilizers, UV-absorbing agents, stericallyhindered amines, metal deactivators, metal oxides, hydroxylamines, dropinhibitors, calcium stearate, zinc stearate, phosphite- and phosphonitestabilizers, UV-absorbing agents of the2-(2′-hydroxyphenyl)benzotriazole and 2-(2-hydroxyphenyl)-1,3,5-triazineclasses, sterically hindered amines and radical formers as well asmixtures thereof.
 6. A polymer moulding material comprising aflame-retardant composition according to claim
 5. 7. A process toprovide flame retardant properties to a polymer, whereby the processcomprises the addition of a) one or more phosphonate compound(s) to saidpolymer and b) one or more 1,3,5-triazine compound(s) to said polymerwherein said one or more phosphonate compounds and said one or more1,3,5-triazine compounds are defined in claim
 1. 8. The processaccording to claim 7, further comprising the addition of a radicalformer.
 9. The polymer, containing a flame-retardant compositionaccording to claim
 5. 10. The polymer according to claim 9, selectedfrom the group consisting of polyolefines, polyesters, polyamides,ABS-polymers, polypropylene, polyethylene, thermoplastic olefine (TPO),high impact polystyrene, thermoplastic polyurethane-elastomers (TPU),polyvinyl chloride (PVC), polyvinyl acetate (PVA), ethyl-vinyl acetate(EVA), polyester resins (UP-Resins), polyurea and polyurethanes ormixtures of two or more thereof.
 11. Articles containing the polymeraccording to claim 9, selected from fibres, films, foils, mouldedobjects and foamed moulding products.